Process of making furnace carbon black and burner therefor



March 4, 1958 N. D. STEELE 2,825,632

PROCESS OF MAKING FURNACE CARBON BLACK AND BURNER THEREFOR Filed April 8, 1952 2 Sheets-Sheet 1Y 1N VEN TOR.

w y m March 4, 1958 N. D. STEELE 2,825,632

PROCESS MAKING FURNACE CRBON BLACK AND BURNER THEREFOR Filed April 8, 1952 2 Sheets-Sheet 2 ,22 l f w //7 i '-0- l/w. l\\\ IN VEN TOR.

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PROCESS F MAKING FURACE CARBN BLACK AND BURNER THEREFOR Application April 8, i952, Serial No. 281,063

3 Claims. (Cl. 2.3-209.8)

This invention relates to processes and apparatus for producing from liquid hydrocarbons carbon black of novel properties and at improved yields. in certain respects this invention is an improvement over that described in the copending application of Friauf et al., Ser. No. 158,226, led April 26, 1950.

To obtain carbon black of desired characteristics at high rates of production and high yields it is necessary to apply the necessary heat to dissociate the liquid hydrocarbonaceous raw material in a particular and carefully' controlled manner. Numerous processes and varieties of apparatus have been devised for the production of carbon black, all operating according to that basic necessity. Of these, many appear to resemble one another but their differences, though often seemingly slight, are of fundamental importance.

ln the carbon black art an improvement over a known process or apparatus which appears as but a modification may in fact lead to an unexpected and important result, whether by way of significant increases in yield of known types of carbon black or by way of producing new types of black not previously known. Such is the case with the process and apparatus of this invention.

, The mechanism of carbon black formation is very complicated and is not fully understood. It is, however, well known that a hydrocarbon does not instantaneously divide itself like an amoeba into its components of carbon and hydrogen under the action of heat but in fact travels through a variety of metamorphoses, polymerizing in the process. Consequently, it makes a great difference how and where the heat is applied to the hydrocarbonaceous raw material.

Generally speaking, the particle size, and hence reinforcing efect, of the carbon black depends upon the speed and duration of the dissociation reaction and upon the environment in which the reaction takes place.

Thus to up grade quality by reducing the particle size of the black or to increase the yield of a known particle size black it is necessary to cause the formation of small particles and to prevent their growth while unreacted hydrocarbon remains in the reaction zone, all without burning any substantial quantity of make raw material. This is accomplished by the novel process and in the novel apparatus of my invention.

Various attempts have been made to supply heat and dilution to the make raw material from a source other than the make material itself. One successful process for doing so is that disclosed in U. S. Letters Patent No. 2,419,565, Krejci, in Which the hydrocarbon raw material is in the vapor state when injected into the reactor. The process of the copending Friauf et al. application referred to above has likewise been successful for the purpose when producing carbon black from make material which is liquid when rst injected into the furnace. Both processes, however, have their limitations as to quality and yield of carbon black and it is to the production of similar and also dierent types of black at improved production rates and yields that this invention relates.

" arent a, rasa Fatented Mar.

Itis an object of this invention to provide an improved process for the production of novel types of carbon black.

Itis also an object of this invention to provide a process for the production of various types of carbon black from liquid hydrocarbons at increased yields.

It is also an object of this invention to provide a process capable of producing known as well as novel types of carbon black at high production rates and yields.

It is also an object of this invention to provide a process in which the requisite amount of heat and diluting gases are efficiently made available upon injection into the furnace of hydrocarbon as a liquid spray.

It is a further object of this invention to provide novel apparatus suitable for accomplishing the above object of this invention.

A feature of the invention comprises a new, simple and inexpensive unitary burner for fuel and make-hydrocarbon with which to establish unique conditions in a carbon black producing reaction zone. This feature of the invention is the subject-matter of my co-pending divisional application Ser. No. 448,257, tiled August 6, 1954.

Broadly, the process of my invention consists in introducing into a suitable carbon black furnace an atomized or vaporized make-hydrocarbon through a single injector pipe centered in the end wall and extending longitudinally of the furnace, simultaneously introducing a combustible fuel gas from a series of points closely surrounding the hydrocarbon injector pipe but at a substantial distance upstream from the point of make-hydrocarbon injection, and owing an oxygen-containing gas past the fuel gas and make-hydrocarbon in sufcient volume to burn all of the fuel gas and a small proportion of the make-hydrocarbon. y

ln this connection a novel burner is employed whichis characterized by a central oil pipe with a discharge nozzle at its end, in combination with a gas pipe concentrically disposed about the oil pipe in spaced relation thereto, and means within the gas pipe for causing gas to ow longitudinally back and forth within the burner in heatexchange relation to the reaction space of the furnace and to be directed so as to envelop the oil spray discharged from the nozzle.

It is important that the fuel gas be introduced in a relatively confined combustion space and at sufficient distance upstream of the point of make-hydrocarbon injection in order that the fuel gas may be substantially completely burned before reaching the hydrocarbon spray. To insure complete burning an excess of air over the theoretical amount required is introduced and hence some small amount of the hydrocarbon will usually be burned as well.

ln fact, it is one of the advantages of my invention that by reason of the critical relationship between the points of introduction of the make oil, fuel gas and air, a wide Variety of operating conditions may be established to produce the many different types of carbon black at a degree of eiciency heretofore not obtained. As the dissociation reaction by which the make-hydrocarbon is converted to carbon black is largely eected by heat transfer from the fuel gas combustion products and since the oxygen containing gas will be air or oxygen diluted with tail gas or other inert gases, there will be a substantialvolume of hot diluent gas to mingle with the make-hydrocarbon and this is effective to prevent growth of the carbon particles.

The desired atmosphere is obtained by the steps of mixing fuel gas and air by jetting the gas into the relativelyr slow moving body of air in a circle immediately around the make-hydrocarbon injector pipe a substantial distance upstream from the point of injection of the makehydrocarbon. There is thus produced a highly turbulent and very hot mass of combustion products flowing past the spray of raw material with resultant heatV transfer to the spray of maximum elciency and concomittantdilution elect.

The process of my invention is particularly adapted to the use of heavy oils and tars, referred to generally herein Aas residual oils, as the source of carbon 'black. Such residual oils are obtained from a wide variety of hydrocarbon distillation and cracking operations, including the vdestructive distillation vof coal. They are characterized by being not fully vaporizable under atmospheric pressure and some of them will crack to carbon beforeas little as 50% vhas gone overhead. Of these I prefer to usethe oilsV having a hydrogen to'carbon ratio of fromabout 0.75 to about 1.25 and a mean molecular weightl of from about 225 tofabou't 550. Such oils will also usually Yhave an A. P. I. gravity of -not more than l0, a viscosity inexcess of 30 SSU (-Saybolt seconds Universal) at .210 Rand a Conradsoncarbonresiduein excess of 1.5.

Typical residual oils useful in the practice of this :invennonare listed 1nA Table I following.

Table I f Aver- Oonradson Viscosity, Ex- Source H/O age A. P. arbon SSU- ample yRatio -Mo1.Wt. Gravity Residue, 210 F.

Percent I Petro- 1.08 391 0.5 17 lw8 leum. II `do 1.1 310.5 0. 5 17.4 135 III -do--. 1.16 250 10. 5 35. 5 IV tlo..y 1.05 440 8.8 20 Y337 V.-. Coal Tar-- 1. 09 277 3. 7 2 l37 VI..-.-- Petro- 1.08 314 1.7 15.3 -84 .leum. VIL--- 'Coal Tar.- 0,'79 399 -'10.'8 24 `112 VIII...-- Ptrog 1. 15 227 3 4 41. 5

eum.

'Ihc various features of my invention will best be understood and appreciated from the following description of atypical embodiment of my novel apparatus by the use -of which the process of my invention may advantageously be carried out, selected for purposes of illustration and shown in the accompanying drawings in which:

Figure 1 is a diagrammatic View, partly in section and partly in side elevation;

, Figure 2 isa View in elevation of the burner; and

Figure 3 is a detail, shown in cross section, ofthe gas head with peripheral orifices and the atomizing ltip.

The furnace herein-shown includes an elongated reac tion chamber 10, which-may be of any convenient cross sectional shape, preferably cylindrical, having -a steel shell 12, a course of insulating brick 14 and a lining 16 of highly refractory material. At the left or inlet-end the reaction-chamber tapers rearwardlyin a section 18 to an inlet passage or lthroatv'zl of leser diameter than that of the reaction chamber 10 of the furnace and which provides a lconfined combustion'space and is the only inlet to the furnace. The taper of thesection '18 is important in that it approximates the angle of the oil spray cone and thus .promotes eicient radiant heat transfer to the oil spray. A burner pipe 22 is centered in the furnace'throat 20 and extends into the furnace and at vleast Yto lthe tapered section .18.

The reaction chamber 10 is open at the endfopposite the burner and with this communicates a conventional iiuepipe 24 `for the passage ofthe gaseous .products of combustion and entrained carbon Vblack to thecollectors and exhaust stack in the usual manner.

The multiple burner of lmy invention through which the make-hydrocarbon oil 'and fuelfgasare introducedzinto the furnace is shown in Figures 2 and 3. This burner: consists of a central oilpipe21-ienclosed concentricallyfora portion of itslength vby azlarger gas .pipe 22-andan er'- tension23 4-having=a-gas tight'capfZS at its-end located within ythe furnace. A -relatively short'pipe 26=is'-c`onf 'centri'cally disposed vapproximately equidistant'between its upstream end into the shouldered inner wall of pipe 22 by a gas tight seal 28 completely around its circumference. This middle pipe 26 is so placed that its downstream end is open to provide a conduit for the passage of gas along the outside of oil pipe 21 and back along the inner surface of extension pipe 23.

Pipe 22 and its extension 23 are connected by/gas head 39 provided With a plurality'of orifices 32 idisposed equidistant from one another around its periphery. Thisrgas -head 30 may be a standard collar, a section of pipeor any other suitable device. The gas pipe'22 Ais extended at its innerend by a long nipple 34 threaded .at one end into the gas pipe and at the other into the cap 25 and having a reducing bushing '36 in its-.outlet end or discharge nozzle.

It can be seen that the burner assembly illustrated is verysimplyfconstructed and can quickly and easily v-be dis- .that parts of different sizes and design can easily be substituted. It will also be readily apparent that thecon.-

struction of the burner may be modied without departing from the spirit of my invention.

For example, pipe 22 could be of continuous length drilled with gas oriices and making possible the omission of gas head 28. Likewise, instead of extending. the oil pipe by the nipple 34 the oil pipe could be continuous. Alternatively, an atomizing nozzle of the ared inlet or orice type may be provided atthe discharge end ofthe oil pipe 21.

The number and size of orifices 32 yare determined largely by the combustion conditions desired. Generally speaking, it is advantageous that as many orifices of as large diameter as possible be provided. However, when extreme turbulence is required fewer orifices of smaller diameter may advantageously be employed. As here shown the orifices are directed radially from the burner pipe but they may be directed downstream atan angle to the radius or helically toimpart a spinning motion to the gases.

Oil pipe-21 terminates outside the furnace in a mixing chamber 40 where the liquid hydrocarbon make material, preferably preheated to improve its uidity, and .supplied through Vinlet pipe 42 is initially aspirated by and .mixed with air, .steam `or other vgaseous atomizing vtluid, or Ymixture thereof, Vintroduced through -pipe 444. The mixing 'chamber 40 may be of any conventional design which employs the two -uidatomization principle. A number of commercial mixers are readily-available andsatisfactory forthepurposes of Amy invention.

Gas `pipe 22 embraces the centraloil -pipe 21k v'for la portion only of its `total length but terminates outside of the furnace in a gas tight :seal 46. Union 48is yprovided for the introductiomof :a combustible gas into the gas stream of the pipe l22.

In operation the make-hydrocarbon atomizedwith a gas such as air, steam ora combustiblefor inert gas, in chamber 40 is discharged from pipe 21 into -thereaction space of the furnace v10 in the form of a conical spray composedvofminute droplets of oil. At the same time a combustible gas such as natural gas, coke oven gas, hydrogen or r`v-a'porized or atomized liquid hydrocarbon isintroducedinto the confined combustion'space'of the furnace through gas head 30 in the zform lof jets that v'are directed radially and outwardly in respect to the projected `axis of the oil spray. Air ows into the furnace under 1ow1pressure (about 4-8 inches of water) from header Y50 supplied-.fromduct 52 through furnace throat 20 Vand thence past lgashead 30. The rate vof air vH ow isdetermined principally gby the rate v'of Afuelggas ilowfand secondarily by the .rate of make-hydrocarbon ow, Vit being the object to supply suiiicient air to'burn ;all.zof the fuelgas anda small vportion-oftheoil. .Thetgas head 30 being 'suiciently far upstream from the oil pipe nozzle to insure that the gas is burned, principally in the confined combustion space provided by the throat 20, before it can make contact with the oil spray. The hot average by almost one pound per gallon of raw material, or by about 20%, a truly significant increase. Furthermore, when yield was not increased by any important amount, the qualities of modulus and abrasion products of combustion then mingle intimately with the resistance were substantially increased. oil spray by virtue of the respective components of ow Having thus disclosed my invention and described in so that the carbon-black-forming reaction occurs almost detail preferred embodiments thereof, I claim and desire simultaneously with the introduction of the oil into the to secure by Letters Patent.: reaction zone. Excess air not needed to burn the t'uel 1. A process of producrng carbon black comprising gas will, of course, burn a small amount of the oil. the steps of owing atomized make .hydrocarbon 111 a The distance between the oil pipe tip and the plane of stream into a reaction space and injecting it as a diorices 32 is subject to considerable variation dependvergent spray, owing a combustible fuel gas 1n an aning upon the characteristics of the carbon black to be oula? Stream enveloping the hydfoefl'bon sQ'eam, revers' produced. It will not ordinarily be less than about 6 111g the dll'eeflofl of gas OYV and dlfeetmg 1t rearwardly inches and may be as great as about 22 inches In any 15 from the divergent spray in a counter current annular event the distance must be sufficient that all or most of stream, dlSChalfgmg he gas of that streafn fw a com' the gas will be burned before reaching the make oil bustion space in radial Jets at a substantial distance upspray but not so far that substantial heat will be lost Sleafn from the Peint of hYdl'oeafbon mleetlon: and from the combustion products before mixing with the bullllng the Combustible fUe1 gas oit Spray 2. The process of producing carbon black as dened Art important feat-ure of the burner of my inventitm in claim 1 further characterized by directing. the com- ,.ie that of circulating the fuel gas to the discharge tip bustible gas into the combustion space in radial Jets be- .and back along the outer conduit in an annular counter tween 6 a1}d 22 Inches Upstream from the Polnt of hy' current stream in contact with the wall of pipe 26 before dfoeabon lnleetloninjection into the furnace through gas head 30. Being t 3- The Pfoeess of PfodUC mg C afbon Mac? as defined exposed to the intense heat generated by the burning 111 elalm 1 further Cha'l'acteflzed 111 that the Jets 0f CCFD fuel the extension pipe 23 would soon fail were it not bustlble fin-e1 eas arefu'efd mm a Confined Combustion for the cooling obtained from the circulating fuel gas. space Vl/ hleh 1s less 111 diameter ih alf she l'eaetlon space At the same time the fuel gas being exposed to the heat luto Whlch the make'hydfocarbon 1s mlectedtransmitted through the walls of pipe 23 is preheated 30 for higher thermal eteieney References Cited in the le of this patent Results obtained by the practice of my invention are UNITED STATES PATENTS Set forth in the following examples of runs illustrative of 1,43 8,032 Frost Der; 5 1922 many made 1n furnaces. 5.65 ft. and 10.65 .ft. 1.11 length. 35 2,292,355 Ayers Aug 11 1942 It will be noted that significant increases in yield were 2,375,795 Krejci May 15, 1945 obtained by the novel process and in the new apparatus 2,375,797 Krejei May 15, 1945 of my invention and that such increased yields were con- 2,375,798 Krejci May 15, 1945 sistently obtained while maintaining and even improv- 2,458,542 Urquhart Jan. 11, 1949 ing the quality of the product. In those cases where 40 2,499,437 Wiegand etal. Mar. 7, 1950 yield was not increased a very great increase in product 2,499,438 Wiegand et al. Mar. 7, 1950 quality, notably in abrasion resistance in rubber, was the 2,529,873 Heller Nov. 14, 1950 usual result. 2,531,316 Zink Nov. 21, 1950 Pro ertlesincold Increase rub er, percent of Make Oil, Fuel Gas, A11', Make Oil, Yield, I2 Surf. Gas Head lnyield standard Run No. gal/hr. O. F. H. MCFJ percent #/gal. area Furnace Size Orices, Standardl over hr. comb. (sq. inJg.) inches std. av.

(#lgal.) Abrasiou 300 res. modulus 60.2 1,988 42.2 22.6 4.33 57 5.65'x18" 12% HAF 0.83 102 125 38 2,913 39.1 14.51 4.08 74 5.65'x18" 12% HAF 0.58 101 111 39 3,000 36.6 8.24 4.60 54 5.65'x18" 12% HAF 1.10 92 109 39.9 2.997 36.5 7.73 4.55 51 5.65'1118" 12% HAF 1.05 10i 113 39.9 4,006 47 7.49 3.88 73 5.65'1118" 12% HAF 0.38 113 114 59 3,998 47.7 6.12 5. 35 44 5.65'218" 12% HAF 1.85 78 112 60.8 3,001 49.1 8.85 3.46 69 10.65'1118" 24% HAF 0.04 112 97 40.1 3,989 47.1 7.94 3.87 71 10.65'218" 24% HAF 0.37 106 94 59.5 4,000 49 7.22 4.79 47 10 65x18" 24% HAF 1, 29 98 95 59.4 3,983 48.4 6.45 4.63 49 10.65x18" 24% HAF 1.13 96 90 69.8 2,998 38.7 6.60 5.28 33 10.65'1127" 12% FEF 1.03 97 116 91.4 2,994 40.7 6.35 5.54 31 10.65'1427" 12% FEF 1.29 92 103 69.7 2,998 33.9 2.02 6.25 27 10.65'227" 12% FEF 2.00 93 106 60.0 3,000 32.6 0.97 5.50 30 10.65' x27" 12% FEF 1.25 105 114 61.2 5.30 5.66 28 10.65'x27" 12% FEF 1.41 98 116 61.7 8.09 4.95 36 10.65'x27'l 12% FEF 0.70 106 117 60.1 8.64 6. 48 36 10.65'x27" 12% FEF 1.23 101 119 6.30 4.55 33 10.65'1127" 12% FEF 0.30 103 114 69.1 11.7 5.02 39 10.65'x27" 12% FEF 0.77 104 108 59.9 9.2 5.60 39 10.65'1127" 12% FEF 1.35 106 118 60.1 9.15 5.29 37 10.65'x27" 12% FEF 1.04 103 113 Nora-1 The standards used are Vulcan 3 for HAF and Sterling SO for FEF, both produced in accordance with the process disclosed and claimed in Friaui et al. application Ser. N o. 158,226. The yield figures for the standard are as follows: HAF-3.51m. per gal. of make oil; FEE-4.25 lbs. per gal.

of make oil.

It is noteworthy that 'by following the process and utilizing commercial size apparatus of this invention .yields of carbon black product were increased on the 75 2,597,992

Loving May 15, 1951 2,564,736

Stokes Aug. 21, 1951 Heller May 27, 1952 

1. A PROCESS OF PRODUCING CARBON BLACK COMPRISING THE STEPS OF FLOWING ATOMIZED MAKE HYDROCARBON IN A STREAM INTO A REACTION SPACE AND INJECTING IT AS A DIVERGENT SPARY, FLOWING A COMBUSTIBLE FUEL GAS IN AN ANNULAR STREAM ENVELOPING THE HYDROCARBON STREAM, REVERSING THE DIRECTION OF GAS FLOW AND DIRECTING IT REARWARDLY FROM THE DIVERGENT SPARY IN A COUNTER CURRENT ANNULAR STREAM, DISCHARGING THE GAS OF THAT STREAM INTO A COMBUSTION SPACE IN RADIAL JETS AT A SUBSTANTIAL DISTANCE UPSTREAM FROM THE POINT OF HYDROGEN INJECTION, AND BURNING THE COMBUSTIBLE FUEL GAS. 